Synthesis of oxygenated carotenoids



Ulllifi No Drawing. Filed Mar. 23, 1960, Ser. No. 16,951 Claims. (Cl. 200-488) Thisinvention relates to the preparation of polyene compounds, and more particularly, to the preparation of pigmenting materials suitable for use in poultry feeds.

For food appeal or merchandizing purposes, it is desirable that poultry and related products not have a pale skin or lack coloration, but rather a more yellow or orangish to red skin coloration. Certain oxygenated carotenoids have been found to the useful for fortifying feeds which contain low levels of natural colorants such as xanthophyll resulting from the substitution of milo or other grains for colorant-containing corn and the like in many commercial feed mixtures. g Such closely related hydrocarbon materials as B-carotene, while being useful for coloring such foods as margarine, do not have utility for pigmenting poultry.

It is an object of this invention to provide a new method for preparing polyene compounds.

tats atent It is another object of this invention to provide a new method for preparing oxygenated carotenoids suitable for use in poultry feeds as pigmenters.

It is another object of this invention to prepare by a novel method dialkoxy carotenoids.

It is another object of this invention to provide a novel method for preparing di-acyloxy carotenoids.

It is still another object of this invention to prepare by a novel method dioxo carotenoids.

'It is likewise another object of this invention to prepare oxygenated carotenoids by a novel one-step process.

These and other objects of the invention are attained by treating certain oxygenated polyene aldehyde compounds with phosphorus pentasulfide in an organic amine solvent medium under substantially anhydrous conditions at an elevated temperature and thereby forming an oxygenated carotenoid.

The oxygenated polyene aldehyde compounds that can be suitably employed as starting materials in the present process have the carbon structure of vitamin A aldehyde with an oxygen-containing radical substituent in the cyclic nucleus, and can be represented by the following struc-' tural formula:

wherein R is an ionyl ring with an oxygen-containing radical substituent, and typically is a monovalent radical having the formula typically having 1 to 18 carbon atoms and preferably 1 to 4 carbon atoms, or an acyloxy radical wherein R" is an alkyl radical typically having 1 to 18 carbon atoms and preferably 1 to 4 carbon atoms. The

oxygenated polyene aldehyde reactants can be employed compounds in a single singlyor in admixture. If only one oxygenated polyene aldehyde reactant is present, the product of the process is a symmetrical carotenoid. However, mixtures of various oxygenated-polyene aldehyde reactants can be employed to prepare mixtures of symmetrical and unsymmetrical carotenoids, as the subject oxygenated polyene aldehydes are highly unsaturated, such compounds can exist in the form of various geometric isomers (i.e., cis and trans isomers) which characterize vitamin A-like compounds. I contemplate the use of any of such geometric isomers in my process. 7

in accordance with the present process the oxygenated polyene aldehydes are treated with phosphorus pentasulfide in an organic amine solvent medium. The tertiary amines are preferred, pyridine being aparticularly eifective solvent medium, although primary and secondary amines can also be utilized. Other suitable amine solvents include 2-picoline, 3-picoline, 4-picoline, diethyl aniline, monoethyl aniline, aniline, quinoline, piperidine, morpholine, dimethylamine, 2,4-lutidine, 2,6-lutidine, 3,4- lutidine, and relatedwell known amines. Likewise, mixtures of more than one amine solvent can be employed. The amount of solvent employed can be widely varied in accordance with usual practice. As phosphorus pentasulfide reacts with water, substantially anhydrous conditionsare employed during the reaction.

The present reaction proceeds to form a carotenoid from the above-described oxygenated polyene aldehydes in the presence of relatively small amounts of the phosphorus pentasulfide. For highest conversions to the carotenoid product, desirably at least .2 mole, and usually .2 mole to 3 moles, of phosphorus pentasulfide for each mole of aldehyde reactant are employed. p

The present reaction is effected at an elevated temperature, usually at least 35 C. and below the temperature at which substantial deterioration or decomposition of the oxygenated carotenoid reaction product takes place, with temperatures in the range of about 50 C. to 125 C. being more usually usedand temperatures in the range of C. to C. being preferred. Under more commonly employed reaction conditions the reaction can be substantially completed in about 1 to 10 hours, although shorter or longer reaction periods may be desired depending on such reaction variables as the reaction temperature, the amount. of agitation, the dilution of the reactants in the reaction solvent, and related reaction variables. The completion of the reaction can be determined by the infrared absorption spectrum of the reaction product.

The reaction product of the oxygenated polyene aldehyde and phosphorus pentasulfide can be worked up or purified by conventional methods. Typical of such methods being solvent extraction, crystallization, and chromatographic adsorption or combinations of more than one purification method. p

In accordance with the present process, the carbon moieties of 2 molar proportions of certain oxygenated polyene aldehydes are joined together to form carotenoid process step as illustrated by the following equation:

Pi lt (amine solvent) While such a reaction of the described oxygenated polyene aldehydes and phosphorus pentasulfide can be readily effected under the conditions described herein, that such a reaction proceeded in such a manner was quite unexpected. It is known in the art that ketones react with phosphorus pentasulfide to form thiones as represented by the following equation:

it R-C-R However, in the present process the carbon moieties of two oxygenated polyene aldehydes join with the splitting out of oxygen rather than the expected substitution of sulfur for oxygen in'the aldehyde reactant to form -a-thial.

The present process is further illustrated by the following examples of preferred embodiments thereof. "I he ultraviolet data set out in the following examples were determined in ethanol. V

Example 1 -.'To a mixture of 0.5 g. of phosphorus pentasulfide and 4 ml. of pyridine was added a solution of 1 g. of 3-acetoxyvitamin A aldehyde in 8 ml. of pyridine con- "taining 0.2 g. of hydroquinoire. The 3-acetoxyvitamin Clix 7 4 aldehyde reactant is described in J. Chem. Soc., page 4909 (1957), and has the following formula CH3 CH9 f After heating the resulting mixture for 1.5 hours at 100 C. under nitrogen, an additional 0.14 g. of phosphorus pentasulfide was added and the heating continued at 100 C. for 4.5 hours. The resulting reaction mixture was 0111' OH; on,

then worked up by the method describedin Example 1 to give 254 mg. ofa canthaxanthin concentrate having E (1%, 1 cm.) (475 m,zr)=36l, canthoxanthin having the formula HsC CH3 A aldehyde reactant is described in D utch P atent No.

25,284 and has the following formula: I 7

me on: g

noon:

The resulting mixture Was heated at 100 C. for 1.5 hours while a slow stream, of nitrogen was bubbled there- ;through. An additional 0.4 g. of phosphorus pentasulfidewas then added and the reaction mixture heated for an additional 4.5 hours at 100 C. After cooling, the resulting solution was decanted from an insoluble mass into 100 ml. of diethyl ether and this other solution .then washed successively with 10%. sulfuric acid, water,

- 0.5 N potassium hydroxide and again with water. After drying over anhydrous sodium sulfate, the solvent wasevaporated to give 814 mg. of a 4,4'-diacetoxy-fi-carotene concentrate having E (1%, 1cm.) (465 m :420, 4,4'- 7 diacetoxyfi-carotene having'the following formula H30 'CH:

on; V cm Similarly, 3,3'-diacetoxy-B-carotene can be prepared if 4acetoxyvitamin'A aldehyde is substituted for the 3-acetoxyvitamin A aldehyde.

Example 2 T0 a mixture of 0.18 g. of phosphorus pentasulfide and 2 ml. of pyridine wasaddeda 4 ml. pyridine solution containing 0.34 g. of a 3-oxovitamin A aldehyde concentrate having E (1%,1l cm.) (292 mg, 375 ma)=3()7, 1126 and 0.1 g. of hydroquinone. The 3-oxovitamin A ,oon;

HaC

Similarly, 3,3'-dioxo-fi-earotene can be prepared if 4- oxovitamin A aldehyde is substitutedfor the 3-oxovitamin A aldehyde.

Example 3 .A. To a mixture of 0.99 g. of phosphorus pentasulfide in 10 ml. of pyridine was added a solution of 20 ml. of pyridine containing 1.8 g. of a 3-methoxyvitamin A aldehyde concentrate having E (1%, 1 cm.) (372 III/1.): 1088 and 0.3 g. of hydroquinone. The 3-methoxyvitamin A aldehyde reactant has the following formula and can be prepared by the method described hereinbelow in part B of this example. ture was heated on a steam bath for one hour. An additional 0.99 g. of phosphorus pentasulfide was added and the steam bath heating was continued for another hour. After cooling, the soluble portion of the reaction Hac- HrCE EJO CH; CH:

HrOf) The resulting mix- 13. Five grams of crystalline all-trans vitamin A aldehyde was dissolved in a mixture of 30 m1. chloroform and 2 ml. anhydrous methanol. This solution was cooled to C. and treated with 3.15 g. N-bromosuccinimide in a mixture of 150 ml. of chloroform and 4 ml. of methanol also at 0 C. The solution was allowed to stand at 0' for min., and then treated with 7.5 g. N-ethymorpholine. The solution was allowed to warm to room temperature over a 3 hr. period, diluted with 300 ml. diether ether and washed successively with cold HCl, 0.5 N. KOH and water. The solution was dried with anhydrous sodium sulfate and evaporated. The yield of product was 6.04 g. This material was dissolved in 100 ml. of petroleum ether (boiling 3060 C.), and chromatographed on 350 g. sodium aluminum silicate adsorbent (Doucil). A weakly adsorbed orange zone.

near the bottom of the column gave, on elution with diethyl ether, 2.0 g. of unreacted vitamin A aldehyde, E (1%, 1 cm.) (378 m )=1245. A more strongly adsorbed yellow zone was eluted to give 3.04 g. of a 3- methoxyvitamin A aldehyde concentrate with E (1%, 1 cm.) (372 mu)==l194.

Example 4 Example 5 To a mixture of 0.5 g. of phosphorus pentasulfide and 4 ml. of monoethyl aniline was added a solution of 1 g. of 3-methoxyvitamin A aldehyde and 0.2 g. of hydroquinone in 6 ml. of monoethyl aniline. The resulting mixture was heated for 1.5 hours on a steam bath, then 0.4 g. more of phosphorus pentasulfide added, and the steam bath heating continued for 3 more hours. On working up the reaction mixture as described in EX- ample 1, a 4,4'-dimethoxy-B-carotene preparation having a reddish glassy color and having E (1%, 1 cm.) (450 m,u)=67 was obtained. Similar results are obtained if aniline is employed as the organic amine solvent in lieu of the monoethyl aniline.

Example 6 H5O CH:

and the oxygenated carotenoid has the formula Hi0 CH2 CH3 OH;

B. The reactant, 3-lauroxyvitamin A aldehyde, was prepared as follows. To a solution of 5 g. of all-trans vitamin A aldehyde and 2 ml. of lauryl alcohol in 30 ml. of chloroform at 0 C. was added a cold (0 C.) solution consisting of 3.15 g. of N-bromosuccinimide and 4 ml. of lauryl alcohol in 150 ml. of chloroform. After 6 minutes, 7.5 g. of N-ethyl morpholine was added to the reaction mixture and the solution allowed to warm to room temperature over a period of 3 hours. After diluting with 100 m1. of diethyl ether, the resulting solution was washed successively with 10% sulfuric acid, 0.5 N potassium hydroxide, and finally with water, and thereafter dried over anhydrous sodium sulfate. The residue obtained after evaporating the solvent was chromatographed on a column of 500 g. of sodium aluminum silicate adsorbent (Doucil) to give 4.7 g. of a strongly adsorbed fraction of S-lauroxyvitamin A aldehyde having E (1%, 1 cm.) (275 m )=733. A second similar chromatographing raised the E (1%, 1 cm.) value to 887. The infrared absorption curve of the prepared sample showed the presence of the carbonyl and ether groups.

Example 7 I A. A mixture of carotenoid pigmenting materials was prepared from a mixture of oxygenated polyene aldehydes prepared as described in part B of this example having E (1%, 1 cm.) (373 m .)=715 and consisting essentially of compounds indicated to have the formulas A 3 g. portion of this mixture of oxygenated polyene aldehydes and 1.4 g. of hydroquinone in 38 ml. of pyridine were added to a mixtureof 3.9 g. of phosphorus pentasulfide in 18 ml. of pyridine, and the resulting'reaction mixture heated for 2 hours at C. in a nitrogen-atmosphere. Thereafter, the pyridine layer was separated by decanting, diluted with ml. of diethyl ether and then washed successively with 10% sulfuric acid, .5 N potassium hydroxide, and water. After drying over anhydrous sodium sulfate, the solvent was removed under vacuum to give 2.1 g. of reddish solid material having E 1%, 1 cm.) (440 m =200 and comprising a mix- CHa ture of 3,3'-dirnethoxy'a-, f3- ZiHd e-CETOEEHBS indicated to sulfuric acid. The resulting propynyl carbinols were have the formulas: p then converted to acetylenic'diol acetals by condensing mo on: a mo on;

/ CH3 CH3 1' CH3 C113 moo on; v mo OOH;

H c out r r are on,

CH; 7 CH3 CH3 CH3 OCH;

.B. The mixture of oxygenated polyene aldehydes used with 7.2 g. of 4,4-dimethoxyV-2 butanone in the presence to prepare the carotenoid pigmenting materials of part of ethylmagnesium bromide in about 100 ml. of diethyl fA of this example were prepared as follows. To 19.2 25 ether by refluxing for about hours, and the resulting g. of a-ionone in .140 ml. of carbon tetrachloride was complex decomposed with 5% sulfuric acid to produce added 18 g. of dibromoethylmethylhydantoin. The mixacetylenic .diol acetals. The acetylenic diol acetals were ture was swirled and heated until a vigorous reaction 00- purified :by chromatographing. on a sodium alumina silicurred. When the reaction subsided, the mixture was cate adsorbent '(Doucil), to yield an 8.2 g. purified refluxed 2 minutes, rapidly cooled to C., and filtered fraction which was selectively reduced to olefinic diol from the solid ethylmethylhydantoin inrthe reaction mix- "acetalsi with hydrogen over .82 g. of 5% palladium catature into a solution of 12.3 g. of anhydrous sodium acclyst on carhon'in 82 C(L'Of 'butanone-2 containing .41 ml. tate in 125 ml. of methanol. The ethylmethylhydantoin of-quiuoline. The reduction was effected in about 20 on the filter was washed with 50 ml; carbon tetrachloride, minutes at about room temperature. After removal of and 50 ml. more of methanolwere added to the comthe hydrogenation catalyst by filtration, the resulting olebined filtrate and washings, which were simmered 2.5 finic diol acetals were refluxed in the presence of .62 m1. hours and let stand at room temperature overnight (about of quinoline and .72 ml. of hydrochloric acid in about 18 hours). The resulting. reaction product was then 50 ml. of methyl ethyl ketone. The resulting mixture Worked-up by water dilution and extraction with diethyl of oxygenated polyenealdehydes having E' (1%, 1 cm.) ether to give-24.8 g. of an oil which was chromatographed 40 (373 m =715 were then reacted with phosphorus on alumina from petroleum ether (boiling 30-60 C.). pentasulfide to prepare the mixture of carotenes as de- The lower zone of the chromatographic column containscribed above in part A" of this example.

ing unreacted oa -ionone was Washed through the column Exam [8 8 and discarded, and the main zone of the chromatographic p column eluted to give 18.8 got an oil having E (1%, The oxygenated Carole-Holds p p in accordance 1 cm.) (225 m 281 m )=458,138 nd a Strong eth with the process of the invention have utility as additives and weak acetate 'ester bands in its infrared spectrum. 0 poultry feed to produce pigmentation of broilers and The resulting product was let stand at room temperature V Q YQ The 0xygenated CaTOieVIIOidS d s d in e overnight (about 18 hours) in 100 ml. of .5 N potassium p 'i id g e amp h n employed in the fe d formulahydroxide in 90% ethanol. The resulting 16.7 g. of oil fi n deseribed below at levels of 36 P Pound of was chromatogra hed f om t ol um th (boiljng'3(} feed, and fed to chickens ad libitum for one Week follow- 60 C.) on a 3.7 x 60 crngsoditun aluminium silicate l a pl PEYiOd of 3 W on p l l difit, (Doucil) column. A lower yellow zone was Washed impart a g t yellow to oranglsh plgmeilllallofl 150 the through the column, giving 12.2 g. of an orange oil havn Of 1. Chickeils- C ns fed n the. ame diet in ing E 1% 1 cm) 223 m 287'm;;)=382,23(),' The a the absence of such oxygenated carotenoids, or if fi-caroreaction mixture gently refluxed 30 minutes more. The

infrared spectrum of the orange oil showed the presence @3116 iS'SIlbSl-ltutBd for the oXygenaledcaTotemiids, v a

of arconjugated ketone at 5.95)., a conjugated double P Skin? The fwd formulation minus h described bond at 6.18;, a methoxy group at 9.11 and a trans additives is as follows: i 7 v j double bond at 1017 confirming that the material was Ingredient: V v 1 Amount, Percent composed of methoxyionones. Based on the analysis, the Ground white hominy 71 79 5 prepared product was indicated to be a mixture of 4- Soybean meal 1554 methoxy-m-ionone and 4-methoxy-e-ionone. The resul Meat Scrap 5, ing methoxyionones were then converted to the mixture Calcium carbonate 4 of oxygenated polyene aldehydes used in the present Molassgs 2,0 process by the general method described in Humphlett Dicalcium phosphate 1 0 and Burness U.S. Patent No. 2,676,990 for preparing Iodized Salt 375 vitamin A aldehyde from (Honour: as follows- A 10 gvitamin A and D fegding 11 J25 portion of the prepared methoxyionones was reacted Vitamin concentrate (Water Soluble) 4 pIOpaIgyl br i and of g }Aanganese ulfate nesium turnings in about 35 ml. of diethyl ether. The reaction was efiected by warming to gentle reflux with '70 V p 100 000 stirring for about 5 minutes, the heat removed and the reaction controlled with anice bath to a gentle reflux for about 30 minutes. Thereafter heat was applied and the D acfivated animal stml resulting magnesium complex was decomposed with 5% Thus the present invention provides a novel, simplified,

Potassium iodide g./ton 5.5'

9 one step method for preparing polyene carotenoids, and more specifically, oxygenated carotenoids from less complex polyene aldehydes.

Conventional nomenclature is used herein with respect to the numbering of the oxygenated radical on the cyclic 5 nucleus of the polyene aldehyde reactants and the carotenoid products. The numbering of the substituents in the cyclic ring of the polyene aldehyde reactants is as follows,

and

X CH3 wherein X is an oxygen-containing radical selected from the group consisting of oxo radicals having the formula 1 :0, alkoxy radicals and acyloxy radicals with phosphorus pentasulfide in an organic amine solvent medium under substantially anhydrous conditions at an elevated temperature to form an oxygenated carotenoid having the formula CH3 CH3 CH3 while the numbering of the substituents in the cyclic rings of the carotenoid products is as follows,

As used herem, the term ionyl ring is a monovalent radical having the carbon structure Although the invention has been described in, detail with particular reference to certain typical embodiments, it will be understood that variations and modifications can be eifected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

H3O CH8 wherein X is an oxygen-containing radical selected from the group consisting of oxo radicals having the formula =0, alkoxy radicals having the formula OR' wherein R is an alkyl radical having 1 to 18 carbon atoms and acyloxy radicals having the formula wherein R" is an alkyl radical having 1 to 18 carbon atoms with phosphorus pentasulfide in an organic amine solvent medium under substantially anhydrous conditions at a temperature in the range of 35 C. to 125 C. to form an oxygenated carotenoid having the formula HsC CH CH3 -.CHa CH3 I claim:

1. The process which comprises treating an oxygenated 60 polyene aldehyde having the formula ROH=OH wherein R is an ionyl ring having a formula selected from the group consisting of HaC CH H30 CH @CH; xgcm 3. The process which comprises treating an oxygenated V polyene aldehyde having the formula H30 CH3 CH3 CH3 (6 wherein X is an oxygen-containing radical selected from the group consisting of 0x0 radicals having the formula =0, alkoxy radicals having the formula --OR' wherein R is an alkyl radical having 1 to 18 carbon atoms and acyloxy radicals having the formula 0 -oiin" at a temperature in the range of 35 C. to 125 C. 'to .form an oxygenated carotenoid having the. formula pentasulfide for each mole of 3-methoxyvitamin A alde- :vitamin A aldehyde with phosphorus pentasulfide in an 1 A aldehyde with phosphorus pentasuifidein an organic 3,033,897 V V l 1 g V r a wherein R" is an alkyl radical having 1 to 18 carbon with phosphorus pentasulfide in an organic amine solvent atoms with phosphorus pentasulfide in an organic amine medium under substantially anhydrousconditions of a solvent medium under substantially anhydrous conditions temperature in the range of 50 C. to 125 C. to form at a temperature in the range of C. to 125 C. to W 3,3'-di rnethoxy-e-carotene. form an oxygenated carotenoid having the formula p 5 no on V s q 7 no on i 3 on: CHr om -on.

x orn 7 r H30 2:

4. 'The process which comprises treating an oxygenated 1 12. The process which comprises treating an oxygenated polyene aldehyde having the formula I polyene aldehyde having the formula n Y on on C on, em ,0 1|

. 1 I 1 ll R,-GH=0H- =VOH-OH=GHG=GHCH CH=CH-C=OHGH=GHO=CHGH i 29 wherein R 1s a mixture of monovalent radicals having the formulas mo on; 7 H 0H3 7 Q and v H3O ogom H3O ogcm with phosphorus pentasulfide in an amine solvent medium under substantially anhydrous conditions at a temperature in the range of 50 C. to 125 C. to form a mixture comprising. 3,3'-dirnethoXy-o-carotene; 3,3'-dirnethoxy-fi-carotene and 3,3'-dimethoXy-e-carotene.

13. The process which comprises treating 3-methoxyvitamin A aldehyde with at least .2 'mole of phosphorus V X CH:

wherein X is an oxygen-containing radical selected from the group consisting of oxo radicals having the/formula :0, alkoxy radicals having the formula OR wherein 25 R is an alkyl radical having 1 'to'18 carbon atoms and acyloxy radicals having the formula wherein R" is an alkyl'radical having 1 to1 8 carbon atoms with phosphorus pentasulfide in. an organic amine solvent medium under substantially anhydrous conditions 7 m on, V V 7 Hi0 an.

X CH3 HaC X 5. The process according to claim 1 wherein the amine hyde in at pyridine solvent medium under substantially solvent medium is a tertiary amine. 4.5 anhydrous conditions at "a temperature in the range of 6. The process according to claimlwherein the amine 80 C. to 120 C. to form 4,4-dimethoXy-B-carotene. solvent medium is pyridine. 14. The process which comprises treating 3-methoxy- 7. The process which comprises treating S-methoxyvitamin A aldehyde with at least .2 mole of phosphorus pentasulfide'for each mole of 3-methoxyvitamin A aldeorgani'c aminesolvent medium under substantially an- 50 hyde in a diethyl' aniline solvent medium under subhydrous conditions at a temperature in the range of 50 ,stantially' anhydrous conditions at a temperature in the C. to 125 0. to form 4,4- -dimethoxy-B-carotene. range of 80 C; to 120 C. to form 4,4-dimethoxy-,6-

8. The process which comprises treating 4-methoxycarotene. V I vitamin A aldehyde with phosphorus pentasulfide in an" 15. The process which comprises treating 3-methoxyorganic amine solvent medium under substantially anvitamin A aldehyde withat least .2 mole of phosphorus hydrous conditions at a temperature in the range of 50 pentasulfide for each mole of 3-methoxyvitamin A alde- C. to 125 C. to .form 3,3'-dimethoxy-;3-carotene. hyde in a monoethyl aniline solvent medium under sub- 9. The process which comprises treating 3-oxovitamiu stantially' anhydrous conditions at a temperature in the range of 80 C. .to 120QC. to form 4,4' dimethoxy-flamine solvent medium undersubstantially anhydrous conso carotene. j V ditions at a temperature in the range of 50 C. to form 16. The process which comprises treating4-methoxy- 4,4'-dioxo- 3-carotene. V vitamin A aldehyde with at least .2 moleof phosphorus 10. The process which comprises treating 3-acetoxypentasulfide for each mole of 4-methoxyvitarnin A aldevitamin A aldehyde with phosphorus pentaslllfidc in a hyde in a pyridine solvent medium under substantially organic'amine solvent medium under substantially ana anhydrous conditions at a temperaturein the range of hy r us conditions at a temperature in the rangeof 50 80 C. to 120 C. to form 3,3'-'dimethoxy 3-carotene.

C. to 125 C- 10 form y-fl-0fl 0tcne. V g 17. The process which comprises treating 3-oxovitar'nin 1 .Th processwhich o p e nsa ys A aldehyde with at least .2 mole of phosphorus pentapolyene aldehyde having the formula V I 330 E a pyridine solvent medium under substantially anhydrous J 1 s C 1 v 7 conditions at a temperature inthe range of C. to

CH=CE--j=CH CH=-Q}ji g=-CH CE C. to'form 4,4' -dioxo-fi-carotene.

' 18. The process which comprises treating 3-acetoxyvitamin A aldehyde with at-least .2 mole of phosphorus HaCO CH3 sulfide for each mole of 3-oxovitamin A aldehyde in a v 75 pentasulfide for each mo ie of 3-acetoxyvitamin' A aldeall \/ CH3 CH3 (III) H30 0 OH3 with at least .2 mole of phosphorus pentasulfide for each mole of said oxygenated polyene aldehyde in a pyridine solvent medium under substantially anhydrous conditions wherein R is a mixture of monovalent radicals having the formula HaC CH3 HsC CH3 and HaCO CH3 H CO- -CH3 with at least .2 mole of phosphorus pentasulfide for each mole of said oxygenated polyene aldehyde in a pyridine solvent medium under substantially anhydrous conditions at a temperature in the range of 80 C. to 120 C. to

at a temperature in the range of Q to 15 form a mixture comprising 3,3-dimethoxy-a-carotene,

form 3,3'-dimethoxy-e-carotene.

20. The process which comprises treating an oxygenated polyene aldehyde having the formula 3,3'-dimethoxy- 3-carotene, tene.

and 3,3'-dimethoxy-e-caro- No references cited.

UNITED STATES P CORRECTION Column 10 shown below lnst lines 2 to 7, ead of as in th [1 c CH3 Signed and sealed this 9th day of October 1962, (SEAL) Attest:

ERNEST w. SWJDER DAVID LADD Attesting Officer Commissioner of Patents 

1. THE PROCESS WHICH COMPRISES TREATING AN OXYGENATED POLYENE ALDEHYDE HAVING THE FORMULA 